CN108862697A - A kind of low-temperature synchronous removes the device and technique of ammonia denitrogenation - Google Patents
A kind of low-temperature synchronous removes the device and technique of ammonia denitrogenation Download PDFInfo
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- CN108862697A CN108862697A CN201810608255.4A CN201810608255A CN108862697A CN 108862697 A CN108862697 A CN 108862697A CN 201810608255 A CN201810608255 A CN 201810608255A CN 108862697 A CN108862697 A CN 108862697A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/11—Turbidity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/14—NH3-N
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/16—Total nitrogen (tkN-N)
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- Environmental & Geological Engineering (AREA)
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Abstract
A kind of low-temperature synchronous removes the device and technique of ammonia denitrogenation, belongs to water process except ammonia denitrogenation technical field, can solve the problems, such as biological denitrificaion low efficiency under the unfavorable conditions such as existing sewage treatment winter or low temperature, include the following steps：Raw water filtration removes particulate matter and organic matter；Put into oxidant pre-oxidation；Pre-oxidation water after filter enters catalyst oxidation reactor, and the water after catalysis oxidation enters fluidized-bed reactor, and for the granular filler in fluidized bed by constituting through the modified active carbon of iron, magnesium, manganese, water outlet is filtered after being passed through air-treatment in bottom.This technique excellent catalytic effect can remove ammonia nitrogen and total nitrogen in water removal simultaneously；It is adapted to catalysis oxidation in low temperature environment and removes ammonia, and do not influenced substantially by pH value, can effectively solve the problems, such as that low-temperature biological denitrification ability is insufficient.
Description
Technical field
The invention belongs to water process to remove ammonia denitrogenation technical field, and in particular to a kind of low-temperature synchronous except ammonia denitrogenation device and
Technique.
Background technique
Ammonia nitrogen is pollutant common in water, there is important influence to aquatile.Ammonia nitrogen height promotes aquatic algae
Growth, the undue growths such as planktonic algae such as blue-green alge cause water quality deterioration.The transmitting of ammonia inhibition fish oxygen, constitutes aquaculture
Risk.Method in water except ammonia is mainly bioanalysis and chemical method.The main method of sewage treatment plant's abatement ammonia nitrogen is raw at present
Object denitrogenation has removal effect good, technical maturity, the advantages such as at low cost.But Nitrogen removal effect is very poor under cryogenic conditions, is the winter
The primary factor that sewage effluents cannot be up to standard during season or low temperature.
The problem of low temperature is except ammonia is very universal, is in urgent need.Yangtze River in China northern area winter time is long, populous,
Industrial intensive, stain disease yield is big.Sewage treatment plant generally faces the problems such as low temperature is except ammonia, denitrogenation.In the world many countries and
The sewage treatment plant in area equally faces the problem of low temperature is except ammonia, denitrogenation.Existing low temperature concentrates at enhanced biological except ammonia technology
Reason, break point chlorination etc..Enhanced biological processing is concentrated mainly on：1）It screens low temperature and removes the micro- life of ammonia except ammonia strain or to existing
Object, which is done, strengthens low temperature except ammonia mutagenesis, genetic modification etc.；2）Extend hydraulic detention time, reduce load, promotes sludge concentration etc.；3）
Heating, heat preservation, promote water temperature etc..Low temperature bacteria selection and mutagenesis etc., are merely resting on the laboratory research stage, and low temperature removes ammonia
Nitric efficiency is low, reaches application requirement far away.Extend hydraulic detention time and promote the way of biomass, is only limitted to relatively low
Temperature（5~10℃）, water below for 5 DEG C is then helpless.Heat temperature raising cost is excessively high.Break point chlorination method using hypochlorous acid with
The reaction of ammonia nitrogen is oxidized removal.But hypochlorous acid（Liquid chlorine, bleaching powder, sodium hypochlorite etc.）A large amount of uses can generate largely
Disinfection by-products that is toxic and having three-induced effect and strong smell.As it can be seen that low temperature removes the problem of ammonia in China's North of Yangtze River
Wide geographic area long-term existence, low temperature is big except ammonia difficulty, and technical need is urgent.
Summary of the invention
The present invention provides aiming at the problem that biological denitrificaion low efficiency under the unfavorable conditions such as existing sewage treatment winter or low temperature
A kind of low-temperature synchronous removes the device and technique of ammonia denitrogenation.
The present invention adopts the following technical scheme that：
A kind of low-temperature synchronous removes the device of ammonia denitrogenation, including water tank inlet, the catalyst oxidation reactor equipped with granular filler, is equipped with
The fluidized-bed reactor and filter of granular filler, water tank inlet are connected by pipeline and the water inlet of catalyst oxidation reactor bottom
It connects, the water outlet at the top of catalyst oxidation reactor is connect by pipeline with the water inlet of fluidized-bed reactor bottom, and fluidized bed is anti-
The water outlet at the top of device is answered to connect by pipe-and-filter, wherein the pipeline between water tank inlet and catalyst oxidation reactor
It is equipped with water pump and valve I, the oxidant storage connected by valve II and spinner flowmeter I is equipped between water pump and valve I
Tank I, the pipeline between catalyst oxidation reactor and fluidized-bed reactor are equipped with valve III and pass through valve IV and rotor stream
The water inlet of the oxidant holding vessel II that meter II connects, catalyst oxidation reactor bottom is equipped with water distributing area I, and catalysis oxidation is anti-
Answer equidistantly set between the granular filler in device there are four aperture as the cellular-plastic panels of 2mm, fluidized-bed reactor bottom into
Water distributing area II is equipped at the mouth of a river, top is equipped with the perforated baffle that aperture is 2mm, the other side of the water distributing area II of fluidized-bed reactor
Equipped with the air pump connected by valve V.
A kind of low-temperature synchronous removes the technique of ammonia denitrogenation, includes the following steps：
The first step, pre-filtering, water sample turbidity to be processed>Particulate matter and particle when 2NTU, in filtering removal pending water sample
After organic matter, into water tank inlet；Work as turbidity<When 2NTU, it is directly entered water tank inlet；
Second step, pre-oxidation, adds oxidant in the water sample to be processed into above-mentioned water tank inlet by oxidant holding vessel I,
Add 2 ~ 4 times that ratio is ammonia nitrogen molar concentration in water sample to be processed, 1 ~ 2min of reaction time；
Third step, catalytic oxidation, the water after pre-oxidation enter catalyst oxidation reactor, and the particle in catalysis oxidation bed is filled out
It under the action of material, is reacted through catalytic bed, reaction time 20min；
4th step, fluidized-bed reaction, the water after catalytic oxidation pass through II supplemental oxidant of oxidant holding vessel, magnitude of recruitment
It is 50% of pre-oxidation throwing amount in second step, into fluidized-bed reactor, by granular filler, bottom is passed through air by air pump,
Residence time 10min；
5th step, is discharged after the micro-filtrate membrane filtration in filter.
Oxidant described in second step and the 4th step is the hydrogenperoxide steam generator of mass concentration 30%.
Granular filler described in third step and the 4th step is by the active carbon composite modified through iron, magnesium, manganese.
The preparation method of the granular filler, includes the following steps：By concentration be 1mol/L iron salt solutions, concentration be
The magnesium salt solution and concentration of 1mol/L is the manganese salt solution of 1mol/L with volume ratio 10:1:5 mixing, with solid-liquid under mixing
Product ratio 1:1（Solid takes apparent volume, and liquid takes volume）The granular activated carbon 15min of partial size 5mm is impregnated, lower be added is mixed
Concentration is the sodium carbonate liquor of 1mol/L, and 10min is mixed in adjustment pH value to 8.0；Active carbon is taken out, is cleaned with pure water, is done
Dry to be placed in Muffle furnace, under conditions of 700 DEG C, anaerobic roasts 2h, obtains granular filler, and wherein molysite is iron chloride or sulphur
Sour iron；Magnesium salts is magnesium chloride or magnesium sulfate；Manganese salt is manganese chloride or manganese sulfate.
Beneficial effects of the present invention are as follows：
1. ammonia nitrogen removal frank of the present invention is high, Nitrogen in Products gasification degree is high, can remove ammonia, denitrogenation simultaneously.
2. adaptability of the present invention is good, dirty Organic substance in water is hardly to catalysis oxidation except ammonia denitrification process impacts.
3. technique is adapted to catalysis oxidation in low temperature environment and removes ammonia, it is insufficient effectively to solve low-temperature biological denitrification ability
Problem.
4. technique is adapted to normal ph（5~9）Sewage in use, be usually not required to adjustment pH value.
5. catalyst etc. is long using the time in technique, metal ion turnover rate is low.
6. technique is simple and direct, small investment, cost of material is low, low energy consumption, meets national society's energy-saving and emission-reduction developing direction.
Detailed description of the invention
Fig. 1 is the apparatus structure schematic diagram that low-temperature synchronous of the present invention removes ammonia denitrogenation；
Wherein：1- water tank inlet；2- catalyst oxidation reactor；3- fluidized-bed reactor；4- filter；5- water pump；6- valve I；
7- valve II；8- spinner flowmeter I；9- oxidant holding vessel I；10- valve III；11- valve IV；12- spinner flowmeter II；
13- oxidant holding vessel II；The water distributing area 14- I；15- cellular-plastic panels；The water distributing area 16- II；17- perforated baffle；18- valve V；
19- air pump.
Specific embodiment
In conjunction with attached drawing, the present invention will be further described.
Granular filler is prepared, the chlorine that compound concentration is 1mol/L respectively ferric chloride solution 1000mL, concentration are 1mol/L
Change magnesium solution 100mL and concentration as the manganese chloride solution 500mL of 1mol/L, takes above-mentioned solution to mix, with solid-liquid under mixing
Than 1:1 impregnated granules active carbon（Partial size 5mm）15min is added dropwise the sodium carbonate liquor of concentration 1mol/L to pH8.0, is mixed
10min；Active carbon is taken out, is placed in Muffle furnace with pure water cleaning, drying, under conditions of 700 DEG C, anaerobic roasts 2h, obtains
To catalytic bed, fluid bed granulate filler.
The apparatus structure schematic diagram of ammonia denitrogenation, catalyst oxidation reactor, fluidized-bed reaction are removed according to Fig. 1 building low-temperature synchronous
Granular filler is separately added into device.
Embodiment 1
In the present embodiment, ammonia nitrogen in water sample to be processed（Ammonium sulfate, pH<5.9）Content is 30mg/L, maintain the temperature at 0 ~
Under the conditions of 4 DEG C, it is respectively catalytic bed 20min, fluidized bed 10min that control flow, which adjusts hydraulic detention time,.Hydrogen peroxide is always thrown
225mg/L is measured, wherein the first toss area 150mg/L, the second toss area 75mg/L.Air throwing amount is 20L/hr.As a result as follows：
It can be seen that at low temperature, it is good using catalysis oxidation ammonia-removal process removal effect of the present invention, and realize synchronous except ammonia, denitrogenation.
Embodiment 2
In the present embodiment, 20 ~ 22 DEG C of room temperature and low temperature are compared（0~5℃）Under the conditions of, above-mentioned catalysis is except the processing of ammonia denitrification process
Effect.Wherein ammonia nitrogen in water sample to be processed（Ammonium sulfate, pH<5.9）Content is 32.8 ~ 33.2mg/L, and control flow is adjusted
Hydraulic detention time is respectively catalytic bed 20min, fluidized bed 10min.The total throwing amount 225mg/L of hydrogen peroxide, wherein first adds
Point 150mg/L, the second toss area 75mg/L.Air throwing amount is 20L/hr.As a result as follows：
As it can be seen that low temperature slightly influences ammonia nitrogen removal, ammonia nitrogen and nitrogen removal rate are omited compared with removal rate under room temperature under cryogenic conditions
There is decline.Even if removal effect overall at low temperature is still very high, ammonia nitrogen removal frank reaches 80% or more, nitrogen removal rate
80% or so.
Embodiment 3
In the present embodiment, above-mentioned low-temperature synchronous removes is added at certain sewage treatment plant's winter second level in ammonia denitrification process system and device
Reason water outlet, wherein ammonia-nitrogen content is 7.2mg/L, total nitrogen content 11.7mg/L, CODcr44mg/L.Maintain the temperature at 2 ~ 5 DEG C of conditions
Under, it is respectively catalytic bed 20min, fluidized bed 10min that control flow, which adjusts hydraulic detention time,.The total throwing amount 210mg/ of hydrogen peroxide
L, wherein the first toss area 140mg/L, the second toss area 70mg/L.Air throwing amount is 20L/hr.After reacting 60min, sampling is surveyed
Test result is ammonia nitrogen 2.6mg/L, total nitrogen content 5.9mg/L, CODcr29.7mg/L.
It can be seen that using catalysis oxidation of the present invention except ammonia effect is obvious under cryogenic conditions, to ammonia under the conditions of 2 ~ 5 DEG C of whole system
Nitrogen, total nitrogen have the synchronous effect removed, also there is certain removal effect to CODcr.
Claims (5)
1. the device that a kind of low-temperature synchronous removes ammonia denitrogenation, it is characterised in that：Including water tank inlet（1）, urging equipped with granular filler
Oxidation device（2）, fluidized-bed reactor equipped with granular filler（3）And filter（4）, water tank inlet（1）Pass through pipeline
With catalyst oxidation reactor（2）The water inlet of bottom connects, catalyst oxidation reactor（2）The water outlet at top passes through pipeline and stream
Fluidized bed reactor（3）The water inlet of bottom connects, fluidized-bed reactor（3）The water outlet at top passes through pipe-and-filter（4）
Connection, wherein water tank inlet（1）And catalyst oxidation reactor（2）Between pipeline be equipped with water pump（5）And valve I（6）, water
Pump（5）And valve I（6）Between be equipped with pass through valve II（7）With spinner flowmeter I（8）The oxidant holding vessel I of connection（9）, urge
Oxidation device（2）And fluidized-bed reactor（3）Between pipeline be equipped with valve III（10）And pass through valve IV（11）
With spinner flowmeter II（12）The oxidant holding vessel II of connection（13）, catalyst oxidation reactor（2）The water inlet of bottom is set
There is water distributing area I（14）, catalyst oxidation reactor（2）In granular filler between equidistantly set there are four aperture as the porous of 2mm
Plastic plate（15）, fluidized-bed reactor（3）The water inlet of bottom is equipped with water distributing area II（16）, it is 2mm's that top, which is equipped with aperture,
Perforated baffle（17）, fluidized-bed reactor（3）Water distributing area II（16）The other side be equipped with pass through valve V（18）The gas of connection
Pump（19）.
2. a kind of low-temperature synchronous of the device using low-temperature synchronous described in claim 1 except ammonia denitrogenation removes the technique of ammonia denitrogenation,
It is characterized in that：Include the following steps：
The first step, pre-filtering, water sample turbidity to be processed>Particulate matter and particle when 2NTU, in filtering removal pending water sample
After organic matter, into water tank inlet；Work as turbidity<When 2NTU, it is directly entered water tank inlet；
Second step, pre-oxidation, adds oxidant in the water sample to be processed into above-mentioned water tank inlet by oxidant holding vessel I,
Add 2 ~ 4 times that ratio is ammonia nitrogen molar concentration in water sample to be processed, 1 ~ 2min of reaction time；
Third step, catalytic oxidation, the water after pre-oxidation enter catalyst oxidation reactor, and the particle in catalysis oxidation bed is filled out
It under the action of material, is reacted through catalytic bed, reaction time 20min；
4th step, fluidized-bed reaction, the water after catalytic oxidation pass through II supplemental oxidant of oxidant holding vessel, magnitude of recruitment
It is 50% of pre-oxidation throwing amount in second step, into fluidized-bed reactor, by granular filler, bottom is passed through air by air pump,
Residence time 10min；
5th step, is discharged after the micro-filtrate membrane filtration in filter.
3. the technique that a kind of low-temperature synchronous according to claim 2 removes ammonia denitrogenation, it is characterised in that：Second step and the 4th step
Described in oxidant be mass concentration 30% hydrogenperoxide steam generator.
4. the technique that a kind of low-temperature synchronous according to claim 2 removes ammonia denitrogenation, it is characterised in that：Third step and the 4th step
Described in granular filler be by the active carbon composite modified through iron, magnesium, manganese.
5. the technique that a kind of low-temperature synchronous according to claim 2 removes ammonia denitrogenation, it is characterised in that：The granular filler
Preparation method includes the following steps：By concentration be 1mol/L iron salt solutions, concentration be 1mol/L magnesium salt solution and concentration be
The manganese salt solution of 1mol/L is with volume ratio 10:1:5 mixing, with solid-liquid volume ratio 1 under mixing:The particle of 1 dipping partial size 5mm
The lower concentration that is added is mixed as the sodium carbonate liquor of 1mol/L in active carbon 15min, and adjustment pH value to 8.0 is mixed
10min；Active carbon is taken out, is placed in Muffle furnace with pure water cleaning, drying, under conditions of 700 DEG C, anaerobic roasts 2h, obtains
To granular filler, wherein molysite is iron chloride or ferric sulfate；Magnesium salts is magnesium chloride or magnesium sulfate；Manganese salt is manganese chloride or sulfuric acid
Manganese.
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| CN201810608255.4A CN108862697B (en) | 2018-06-13 | 2018-06-13 | Device and process for synchronously removing ammonia and nitrogen at low temperature |
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| CN201810608255.4A CN108862697B (en) | 2018-06-13 | 2018-06-13 | Device and process for synchronously removing ammonia and nitrogen at low temperature |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349257A (en) * | 2020-10-13 | 2022-04-15 | 同济大学 | Sewage treatment method based on MBR process |
| CN115353256A (en) * | 2022-08-22 | 2022-11-18 | 山东华城工程技术有限公司 | Water purification treatment process for micro-polluted surface water source water |
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